Theoretical Evaluation of the Molecular Inclusion Process between Chlordecone and Cyclodextrins: A New Method for Mitigating the Basis Set Superposition Error in the Case of an Implicit Solvation Model

2020 ◽  
Vol 60 (4) ◽  
pp. 2115-2125
Author(s):  
Juan José Gamboa-Carballo ◽  
Anthuan Ferino-Pérez ◽  
Vijay Kumar Rana ◽  
Joëlle Levalois-Grützmacher ◽  
Sarra Gaspard ◽  
...  
Keyword(s):  
New Method ◽  
Basis Set ◽  
Implicit Solvation ◽  
Solvation Model ◽  
Theoretical Evaluation ◽  
Basis Set Superposition Error ◽  
Inclusion Process ◽  
Implicit Solvation Model ◽  
Molecular Inclusion

scholarly journals r2SCAN-3c: An Efficient “Swiss Army Knife” Composite Electronic-Structure Method

2020 ◽  
Author(s):  
Stefan Grimme ◽  
Andreas Hansen ◽  
Sebastian Ehlert ◽  
Jan-Michael Mewes
Keyword(s):  
Electronic Structure ◽  
Density Functional ◽  
Chemical Space ◽  
Noncovalent Interactions ◽  
New Method ◽  
Basis Set ◽  
Basis Set Superposition Error ◽  
Benchmark Database ◽  
The Cost ◽  
Conformational Energies

The recently proposed second revision of the SCAN meta-GGA density-functional approximation (DFA) {Furness et al., J. Phys. Chem. Lett. 2020, 11, 8208-8215, termed r<sup>2</sup>SCAN} is used to construct an efficient composite electronic-structure method termed r<sup>2</sup>SCAN-3c, expanding the "3c'' series (hybrid: HSE/PBEh-3c, GGA: B97-3c, HF: HF-3c) to themGGA level. To this end, the unaltered r<sup>2</sup>SCAN functional is combined with a tailor-made <br>triple-zeta Gaussian AO-basis as well as with refitted D4 and gCP corrections for London-dispersion and basis-set superposition error. The performance of the new method is evaluated for the GMTKN55 thermochemical database covering large parts of chemical space with about 1500 <br>data points, as well as additional benchmarks for noncovalent interactions, organometallic reactions, lattice energies of organic molecules and ices, as well as for the adsorption on polar salt and non-polar coinage-metal surfaces. These comprehensive tests reveal a spectacular performance and robustness of r<sup>2</sup>SCAN-3c for reaction energies and noncovalent interactions in molecular and periodic systems, as well as outstanding conformational energies, and consistent structures. At just one tenth of the cost, r<sup>2</sup>SCAN-3c provides one of the best results of all semi-local DFT/QZ methods ever tested for the GMTKN55 benchmark database. Specifically for reaction and conformational energies as well as for noncovalent interactions, the new method outperforms hybrid-DFT/QZ approaches, compared to which the computational savings are even larger (factor 100-1000).<br>In relation to other "3c'' methods, r<sup>2</sup>SCAN-3c by far surpasses the accuracy of its predecessor B97-3c at only about twice the cost. The perhaps most relevant remaining systematic deviation of r<sup>2</sup>SCAN-3c is due to self-interaction-error, owing to its mGGA nature. However, SIE is notably reduced compared to other (m)GGAs, as is demonstrated for several examples. After all, this remarkably efficient and robust method is chosen as our new group default, replacing previous low-level DFT and partially even expensive high-level methods in most standard applications for systems with up to several hundreds of atoms.<br><br>

scholarly journals r2SCAN-3c: An Efficient “Swiss Army Knife” Composite Electronic-Structure Method

2020 ◽  
Author(s):  
Stefan Grimme ◽  
Andreas Hansen ◽  
Sebastian Ehlert ◽  
Jan-Michael Mewes
Keyword(s):  
Electronic Structure ◽  
Density Functional ◽  
Chemical Space ◽  
Noncovalent Interactions ◽  
New Method ◽  
Basis Set ◽  
Basis Set Superposition Error ◽  
Benchmark Database ◽  
The Cost ◽  
Conformational Energies

The recently proposed second revision of the SCAN meta-GGA density-functional approximation (DFA) {Furness et al., J. Phys. Chem. Lett. 2020, 11, 8208-8215, termed r<sup>2</sup>SCAN} is used to construct an efficient composite electronic-structure method termed r<sup>2</sup>SCAN-3c, expanding the "3c'' series (hybrid: HSE/PBEh-3c, GGA: B97-3c, HF: HF-3c) to themGGA level. To this end, the unaltered r<sup>2</sup>SCAN functional is combined with a tailor-made <br>triple-zeta Gaussian AO-basis as well as with refitted D4 and gCP corrections for London-dispersion and basis-set superposition error. The performance of the new method is evaluated for the GMTKN55 thermochemical database covering large parts of chemical space with about 1500 <br>data points, as well as additional benchmarks for noncovalent interactions, organometallic reactions, lattice energies of organic molecules and ices, as well as for the adsorption on polar salt and non-polar coinage-metal surfaces. These comprehensive tests reveal a spectacular performance and robustness of r<sup>2</sup>SCAN-3c for reaction energies and noncovalent interactions in molecular and periodic systems, as well as outstanding conformational energies, and consistent structures. At just one tenth of the cost, r<sup>2</sup>SCAN-3c provides one of the best results of all semi-local DFT/QZ methods ever tested for the GMTKN55 benchmark database. Specifically for reaction and conformational energies as well as for noncovalent interactions, the new method outperforms hybrid-DFT/QZ approaches, compared to which the computational savings are even larger (factor 100-1000).<br>In relation to other "3c'' methods, r<sup>2</sup>SCAN-3c by far surpasses the accuracy of its predecessor B97-3c at only about twice the cost. The perhaps most relevant remaining systematic deviation of r<sup>2</sup>SCAN-3c is due to self-interaction-error, owing to its mGGA nature. However, SIE is notably reduced compared to other (m)GGAs, as is demonstrated for several examples. After all, this remarkably efficient and robust method is chosen as our new group default, replacing previous low-level DFT and partially even expensive high-level methods in most standard applications for systems with up to several hundreds of atoms.<br><br>

Improved Efficiency of Replica Exchange Simulations through Use of a Hybrid Explicit/Implicit Solvation Model

2006 ◽  
Vol 2 (2) ◽  
pp. 420-433 ◽  
Author(s):  
Asim Okur ◽  
Lauren Wickstrom ◽  
Melinda Layten ◽  
Raphäel Geney ◽  
Kun Song ◽  
...  
Keyword(s):  
Replica Exchange ◽  
Implicit Solvation ◽  
Solvation Model ◽  
Implicit Solvation Model

scholarly journals KECSA-Movable Type Implicit Solvation Model (KMTISM)

2015 ◽  
Vol 11 (2) ◽  
pp. 667-682 ◽  
Author(s):  
Zheng Zheng ◽  
Ting Wang ◽  
Pengfei Li ◽  
Kenneth M. Merz
Keyword(s):  
Implicit Solvation ◽  
Solvation Model ◽  
Implicit Solvation Model

scholarly journals Assessment of Constant-Potential Implicit Solvation Calculations of Electrochemical Energy Barriers for H2 evolution on Pt

2018 ◽  
Author(s):  
Maxime Van den Bossche ◽  
Egill Skúlason ◽  
Christoph Rose-Petruck ◽  
Hannes Jonsson
Keyword(s):  
Electrostatic Interactions ◽  
Computational Cost ◽  
Electrochemical Reactions ◽  
Critical Importance ◽  
Theoretical Estimation ◽  
H2 Evolution ◽  
Implicit Solvation ◽  
Solvation Model ◽  
Implicit Solvation Model ◽  
Constant Potential

Theoretical estimation of the activation energy of electrochemical reactions is of critical importance but remains challenging. In this work, we address the usage of an implicit solvation model for describing hydrogen evolution reaction steps on Pt(111) and Pt(110), and compare with the `extrapolation' approach as well as single-crystal measurements. We find that both methods yield qualitatively similar results, which are in fair agreement with the experimental data. Care should be taken, however, in addressing spurious electrostatic interactions between periodically repeated slabs in the VASPsol implementation. Considering the lower computational cost and higher flexibility of the implicit solvation approach, we expect this method to become a valuable tool in electrocatalysis.<br>

scholarly journals r2SCAN-3c: An Efficient “Swiss Army Knife” Composite Electronic-Structure Method

2020 ◽  
Author(s):  
Stefan Grimme ◽  
Andreas Hansen ◽  
Sebastian Ehlert ◽  
Jan-Michael Mewes
Keyword(s):  
Electronic Structure ◽  
Density Functional ◽  
Chemical Space ◽  
Noncovalent Interactions ◽  
New Method ◽  
Basis Set ◽  
Basis Set Superposition Error ◽  
Benchmark Database ◽  
The Cost ◽  
Conformational Energies

The recently proposed second revision of the SCAN meta-GGA density-functional approximation (DFA) {Furness et al., J. Phys. Chem. Lett. 2020, 11, 8208-8215, termed r<sup>2</sup>SCAN} is used to construct an efficient composite electronic-structure method termed r<sup>2</sup>SCAN-3c, expanding the "3c'' series (hybrid: HSE/PBEh-3c, GGA: B97-3c, HF: HF-3c) to themGGA level. To this end, the unaltered r<sup>2</sup>SCAN functional is combined with a tailor-made <br>triple-zeta Gaussian AO-basis as well as with refitted D4 and gCP corrections for London-dispersion and basis-set superposition error. The performance of the new method is evaluated for the GMTKN55 thermochemical database covering large parts of chemical space with about 1500 <br>data points, as well as additional benchmarks for noncovalent interactions, organometallic reactions, lattice energies of organic molecules and ices, as well as for the adsorption on polar salt and non-polar coinage-metal surfaces. These comprehensive tests reveal a spectacular performance and robustness of r<sup>2</sup>SCAN-3c for reaction energies and noncovalent interactions in molecular and periodic systems, as well as outstanding conformational energies, and consistent structures. At just one tenth of the cost, r<sup>2</sup>SCAN-3c provides one of the best results of all semi-local DFT/QZ methods ever tested for the GMTKN55 benchmark database. Specifically for reaction and conformational energies as well as for noncovalent interactions, the new method outperforms hybrid-DFT/QZ approaches, compared to which the computational savings are even larger (factor 100-1000).<br>In relation to other "3c'' methods, r<sup>2</sup>SCAN-3c by far surpasses the accuracy of its predecessor B97-3c at only about twice the cost. The perhaps most relevant remaining systematic deviation of r<sup>2</sup>SCAN-3c is due to self-interaction-error, owing to its mGGA nature. However, SIE is notably reduced compared to other (m)GGAs, as is demonstrated for several examples. After all, this remarkably efficient and robust method is chosen as our new group default, replacing previous low-level DFT and partially even expensive high-level methods in most standard applications for systems with up to several hundreds of atoms.<br><br>

Assessment of Constant-Potential Implicit Solvation Calculations of Electrochemical Energy Barriers for H2 evolution on Pt

2018 ◽  
Author(s):  
Maxime Van den Bossche ◽  
Egill Skúlason ◽  
Christoph Rose-Petruck ◽  
Hannes Jonsson
Keyword(s):  
Electrostatic Interactions ◽  
Computational Cost ◽  
Electrochemical Reactions ◽  
Critical Importance ◽  
Theoretical Estimation ◽  
H2 Evolution ◽  
Implicit Solvation ◽  
Solvation Model ◽  
Implicit Solvation Model ◽  
Constant Potential

Theoretical estimation of the activation energy of electrochemical reactions is of critical importance but remains challenging. In this work, we address the usage of an implicit solvation model for describing hydrogen evolution reaction steps on Pt(111) and Pt(110), and compare with the `extrapolation' approach as well as single-crystal measurements. We find that both methods yield qualitatively similar results, which are in fair agreement with the experimental data. Care should be taken, however, in addressing spurious electrostatic interactions between periodically repeated slabs in the VASPsol implementation. Considering the lower computational cost and higher flexibility of the implicit solvation approach, we expect this method to become a valuable tool in electrocatalysis.<br>

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